EP4304951A1 - Home compostable and degradable extrusion coated substrates - Google Patents

Home compostable and degradable extrusion coated substrates

Info

Publication number
EP4304951A1
EP4304951A1 EP22713804.7A EP22713804A EP4304951A1 EP 4304951 A1 EP4304951 A1 EP 4304951A1 EP 22713804 A EP22713804 A EP 22713804A EP 4304951 A1 EP4304951 A1 EP 4304951A1
Authority
EP
European Patent Office
Prior art keywords
poly
coated substrate
extrusion coated
extrusion
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22713804.7A
Other languages
German (de)
French (fr)
Inventor
Arne Matthew Terwillegar
Karson Durie
John Moore
Joe B. Grubbs III
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Danimer Ipco LLC
Original Assignee
Danimer Ipco LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Danimer Ipco LLC filed Critical Danimer Ipco LLC
Priority claimed from PCT/US2022/019672 external-priority patent/WO2022192486A1/en
Publication of EP4304951A1 publication Critical patent/EP4304951A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G19/00—Table service
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/154—Coating solid articles, i.e. non-hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0068—Permeability to liquids; Adsorption
    • B29K2995/0069—Permeability to liquids; Adsorption non-permeable

Definitions

  • This disclosure relates to compostable polymeric compositions. More particularly, this disclosure relates to home compostable and/or marine degradable substrates having a compostable extrusion coating.
  • Disposable food service items are particularly convenient for serving food at large gatherings of people and at outdoor dining events.
  • Disposable food service items may readily be fabricated from substrates such as paperboard which decompose relatively quickly when composted.
  • substrates such as paperboard which decompose relatively quickly when composted.
  • a simple, uncoated paperboard substrate generally performs poorly as a food service item because the paperboard will rapidly soak up water and/or grease, which ultimately compromises the strength of the paperboard.
  • food service items made from paperboard are typically coated with a thin polymer layer to improve water and grease resistance.
  • Coating made from polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET) may significantly improve the resistance of the paperboard to water and/or grease absorption; however, such polymers do not readily degrade or when composted.
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • this extrusion coated substrate includes a paperboard substrate having at least a first side.
  • the extrusion coated substate also includes a layer of an extrusion coating applied over at least a portion of the first side.
  • This extrusion coating is made up of from about 30 to about 99.5 weight percent of at least one poly(hydroxyalkanoate), and from about 5 weight percent to about 69.5 weight percent of at least one compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
  • the extrusion coating is preferably made up of from about 50 to about 69.5 weight percent of the at least one poly(hydroxyalkanoate).
  • the at least one poly(hydroxyalkanoate) preferably includes poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate (“P(3HB-co- 3HHx)”). More particularly, in certain embodiments, the P(3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. More preferably, the P(3HB-co-3HHx) preferably is made up of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
  • the extrusion coating is preferably made up of from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxy decanoate.
  • the at least one poly(hydroxyalkanoate) is preferably a terpolymer made up from about 75 to about 99.9 mole percent monomer residues of 3- hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3- hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
  • the at least one poly(hydroxyalkanoate) preferably has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
  • the extrusion coating may in some instances include an additional compostable polymer.
  • the extrusion coating preferably includes from about 30.5 weight percent to about 49.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and any mixtures thereof. More preferably, the compostable polymer is made up of poly(lactic acid).
  • the extrusion coating may also include minor amounts of various additives as well.
  • the extrusion coating also includes from about 0.05 weight percent to about 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • the extrusion coating includes from about 0.1 weight percent to about 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • the extrusion coating preferably includes from about 1 weight percent to about 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • the extrusion coating also includes from about 0.1 weight percent to about 50 weight percent of at least one compostable impact modifier which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2-ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1,2, 3 -triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), sebacic acid, azelaic acid, cyclohexan
  • TMPD 2-(hydroxy
  • the impact modifier may comprise a polyester made up of at least three different type of monomer residues, which are derived from: (1) isosorbide; (2) succinic acid or anhydride; and (3) 1,3-propanediol.
  • the extrusion coating preferably exhibits a melt flow rate of about 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTM D1238-13.
  • the extrusion coating is applied over the substrate first side at a coating weight from about 10 to about 50 grams per square meter.
  • the paperboard substrate is made up of Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
  • SBS solid bleached sulfate
  • the extrusion coated substrate is preferably formed into a cup, a plate, straw, or a food container.
  • the properties of extrusion coating have been found to be well-suited to such food service uses.
  • the coating preferably exhibits a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter. Further, the coating preferably exhibits a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5. The coating also preferably exhibits a Dyne value greater than 38, measured according to ASTM D2578-04a. [024] In accordance with the present disclosure, it is also preferred that the extrusion coated substrate is home compostable, as determined by ASTM D6868, and/or that the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
  • the present disclosure first provides a home compostable and/or marine degradable extrusion coated substrate.
  • the substrate is typically paper or a paperboard web.
  • the paper or paperboard for the substrate comprises Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
  • the basis weight for the paper or paperboard substrate is typically at least 400 grams per square meter (gsm) and is more preferably from about 100 gsm to about 400 gsm.
  • the paperboard substrate typically has a thickness from about 1 pt to about 46 pt caliper (about 0.03 mm to about 1.17 mm) and is more preferably from about 5 pt to about 20 pt caliper (about 0.17 mm to about 0.51 mm).
  • the paperboard substrate includes a first side and a second side. At least the first side of the substrate is coated with the extrusion coating. In some embodiments, both the first side and the second side of the substrate are coated with the extrusion coating.
  • the extrusion coating which is applied to the first and optionally the second side of the substrate according to the present disclosure is preferably home compostable as defined by ASTM D6868.
  • the extrusion coating is also biodegradable as defined by ASTM standard D5988.
  • the extrusion coating comprises at least one poly(hydroxyalkanoate) which is compostable, as well as at least one additional compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), poly(ethylene sebicate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
  • the amount of the at least one poly(hydroxyalkanoate) in the extrusion coating is generally from about 30 to about 99.5 weight percent of the extrusion coating. More preferably, the extrusion coating is preferably made up of from about 50 to about 69.5 weight percent of the at least one poly(hydroxyalkanoate). [031] A wide range of one poly(hydroxyalkanoates) may be incorporated into the extrusion coating. In some instances, the at least one poly(hydroxyalkanoate) preferably includes poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate (“P(3HB-co-3HHx)”).
  • the P(3HB-co-3HHx) preferably comprises from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. Even more preferably, this P(3HB-co-3HHx) comprises of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
  • the poly(hydroxyalkanoate) may comprise larger monomer units.
  • the extrusion coating preferably comprises from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
  • the poly(hydroxyalkanoate) may comprise a terpolymer.
  • the at least one poly(hydroxyalkanoate) is preferably a terpolymer comprising from about 75 to about 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3 -hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
  • the weight average molecular weight of the at least one poly(hydroxyalkanoate) will preferably range from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
  • the extrusion coating also comprises at least one compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebicate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
  • the extrusion coating comprises from about 5 weight percent to about 69.5 weight percent of this additional compostable polymer.
  • the extrusion coating may in some instances include an additional compostable polymer.
  • the extrusion coating more preferably comprises from about 30.5 weight percent to about 49.5 weight percent of the at least one compostable polymer.
  • the additional compostable polymer may be selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
  • the compostable polymer more preferably comprises poly(lactic acid).
  • the extrusion coating is a blend of poly(lactic acid) with one or more poly(hydroxyalkanoates).
  • the extrusion coating may also include minor amounts of various additives.
  • the extrusion coating also comprises from about 0.05 weight percent to about 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • the extrusion coating also preferably comprises from about 0.1 weight percent to about 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • the extrusion coating may also comprise from about 1 weight percent to about 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • the extrusion coating may also comprise from about 0.1 weight percent to about 50 weight percent of at least one impact modifier.
  • the impact modifier is preferably a compostable polymer which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2-ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1,2, 3 -triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), se
  • TMPD 2-(hydroxymethyl)-2
  • the extrusion coated substrate is formed by first providing a charge of the extrusion coating polymer mixture.
  • the components of the extrusion coating are combined beforehand and provided in the form of a pelletized resin.
  • a charge of this polymer resin is heated in an extruder to a temperature at or above the melting point of the polymer resin.
  • the exact temperature to which the polymer resin is heated may vary somewhat, depending upon the precise make-up of the polymer resin (the type of compostable polymer, the molecular weight of the compostable polymer, the amount of additives, etc).
  • the polymer resin is heated to a temperature from about 125 °C to about 280 °C, and more preferably heated to a temperature from about 135 °C to about 200 °C.
  • the polymer resin charge is then extruded through a die and applied over a first surface of the substrate.
  • a substantially similar process may be used to apply a coating over the second surface of the substrate as well.
  • the extrusion coating preferably exhibits a melt flow rate of about 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTM D1238-13.
  • the extrusion coating is applied over the substrate first side at a coating weight from about 10 to about 50 grams per square meter.
  • the finished substrates according to the present disclosure may be used to form a variety of end products.
  • the extrusion coated substrates are particularly well suited to for conversion to form food services items.
  • the extrusion coated substrates may be formed into a cup, a plate, or a food container.
  • the extrusion coated substrates may be converted to form cartons, bottles, straws, boxes, or containers.
  • the extrusion coated substrates according to the present disclosure are well- suited to use for food applications.
  • the coated substrates exhibit good resistance to oil, grease and to water.
  • the extrusion coated substrates of the present disclosure preferably exhibit a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter. Further, the extrusion coated substrates preferably exhibit a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5. Moreover, the extrusion coated substrates also preferably exhibit a Dyne value greater than 38, measured according to ASTM D2578-04a.
  • the extrusion coated substrates of the present disclosure are home-compostable, unlike substrates coated with conventional petroleum-based polymers.
  • the extrusion-coated substrate is home compostable, as determined by ASTM D6868, and/or that the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
  • Embodiment 1 A home compostable and/or marine degradable extrusion coated substrate comprising:
  • Embodiment 2 from 5 weight percent to 69.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), poly(ethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
  • Embodiment 2 The extrusion coated substrate of Embodiment 1, wherein the extrusion coating comprises from 50 to 69.5 weight percent of the at least one poly(hydroxyalkanoate).
  • Embodiment 3 The extrusion coated substrate of Embodiments 1 or 2, wherein the at least one poly(hydroxyalkanoate) comprises poly-3 -hydroxybutyrate-co-3 - hydroxyhexanoate (“P(3HB-co-3HHx)”).
  • Embodiment 4 The extrusion coated substrate of Embodiment 3, wherein the P(3HB-co-3HHx) comprises from 75 to 99 mole percent hydroxybutyrate and from 1 to 25 mole percent hydroxyhexanoate.
  • Embodiment 5 The extrusion coated substrate of Embodiment 3, wherein the P(3HB-co-3HHx) preferably comprises from 93 to 98 mole percent hydroxybutyrate and from 2 to 7 mole percent hydroxyhexanoate.
  • Embodiment 6 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating comprises from 1 to 25 weight percent of at least one polyhydroxyalkanoate comprising from 25 to 50 mole percent of hydroxyvalerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
  • Embodiment 7 The extrusion coated substrate of any of the preceding embodiments, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from 75 to 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from 0.1 to 25 mole percent monomer residues of 3 -hydroxyhexanoate, and from 0.1 to 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
  • the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from 75 to 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from 0.1 to 25 mole percent monomer residues of 3 -hydroxyhexanoate, and from 0.1 to 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
  • Embodiment 8 The extrusion coated substrate of any of the preceding embodiments, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 50,000 Daltons to 2.5 million Daltons, as determined by ASTM D5296-05.
  • Embodiment 9 The extrusion coated substrate of any of the preceding embodiments, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 500,000 Daltons to 750,000 Daltons, as determined by ASTM D5296-05.
  • Embodiment 10 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating comprises from 30.5 weight percent to 49.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and any mixtures thereof.
  • compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and any mixtures thereof.
  • Embodiment 11 The extrusion coated substrate of any of the preceding embodiments, wherein the at least one compostable polymer comprises poly(lactic acid).
  • Embodiment 12 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 0.05 weight percent to 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • Embodiment 13 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 0.1 weight percent to 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • Embodiment 14 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 1 weight percent to 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • Embodiment 15 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 0.1 weight percent to 50 weight percent of at least one impact modifier which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2- ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1,2, 3 -triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), sebacic acid
  • Embodiment 16 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating exhibits a melt flow rate of 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTMD 1238-13.
  • Embodiment 17 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating is applied over the substrate first side at a coating weight from 10 to 50 grams per square meter.
  • Embodiment 18 The extrusion coated substrate of any of the preceding embodiments, wherein the paperboard substrate comprises Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
  • the paperboard substrate comprises Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
  • SBS solid bleached sulfate
  • Embodiment 19 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coated substrate is formed into a cup, a plate, straw, or a food container.
  • Embodiment 20 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating exhibits a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter.
  • Embodiment 21 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating exhibits a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5.
  • Embodiment 22 The extrusion coated substrate of any of the preceding embodiments, wherein the coating exhibits a Dyne value greater than 38, measured according to ASTM D2578-04a.
  • Embodiment 23 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coated substrate is home compostable, as determined by ASTM D6868.
  • Embodiment 24 The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
  • EXAMPLE 8 [096] To a 40 mm extruder, a mixture of 58.9% 2 mol% PHA, 40% polylactic acid, 0.1% 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane, and 1% pentaerythritol was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
  • Example 1 The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 15 pounds/ream.
  • the subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s). Furthermore, the coating exhibits a Cobb test value of 0.17 - 0.21, a Kit test value of 10+, and a Dyne value of 42-44.
  • Example 1 The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 12 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
  • Example 1 The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 9 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
  • EXAMPLE 13 [0106] The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 6 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
  • Example 9 The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 15 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
  • Example 9 The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 12 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
  • Example 9 The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 9 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
  • Example 9 The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 6 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).

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Abstract

The present disclosure provides a home compostable extrusion coated substrate which includes a paperboard substrate having at least a first side and a layer of an extrusion coating applied over at least a portion of the first side. This extrusion coating is made up of from about 30 to about 99.5 weight percent of at least one poly(hydroxyalkanoate), and from about 5 weight percent to about 69.5 weight percent of at least one compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebicate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof. Preferably, in accordance with the present disclosure, it is also preferred that the extrusion coated substrate is home compostable, as determined by ASTM D6868.

Description

HOME COMPOSTABLE AND DEGRADABLE EXTRUSION COATED SUBSTRATES
FIELD
[001] This disclosure relates to compostable polymeric compositions. More particularly, this disclosure relates to home compostable and/or marine degradable substrates having a compostable extrusion coating.
BACKGROUND
[002] For the sake of convenience, consumers frequently use disposable food service items, such as plates, bowls, cups, takeout containers, straws and other eating or drinking utensils. Disposable food service items are particularly convenient for serving food at large gatherings of people and at outdoor dining events.
[003] Disposable food service items may readily be fabricated from substrates such as paperboard which decompose relatively quickly when composted. However, a simple, uncoated paperboard substrate generally performs poorly as a food service item because the paperboard will rapidly soak up water and/or grease, which ultimately compromises the strength of the paperboard. As a result, food service items made from paperboard are typically coated with a thin polymer layer to improve water and grease resistance.
[004] Coating made from polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET) may significantly improve the resistance of the paperboard to water and/or grease absorption; however, such polymers do not readily degrade or when composted.
[005] It would be desirable to provide a new coating for food service items which is fully home compostable, especially if this compostable coating provided good water and grease resistance - i.e., water and grease resistance comparable to that provided by conventional, non-compostable coatings.
SUMMARY OF THE INVENTION
[006] The above and other needs are met by a home compostable extrusion coated substrate according to the present disclosure.
[007] In a first aspect, the present disclosure provides a home compostable and/or marine degradable extrusion coated substrate. According to one embodiment, this extrusion coated substrate includes a paperboard substrate having at least a first side. The extrusion coated substate also includes a layer of an extrusion coating applied over at least a portion of the first side. This extrusion coating is made up of from about 30 to about 99.5 weight percent of at least one poly(hydroxyalkanoate), and from about 5 weight percent to about 69.5 weight percent of at least one compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
[008] According to certain embodiment, the extrusion coating is preferably made up of from about 50 to about 69.5 weight percent of the at least one poly(hydroxyalkanoate).
[009] Further, according to some embodiments, the at least one poly(hydroxyalkanoate) preferably includes poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate (“P(3HB-co- 3HHx)”). More particularly, in certain embodiments, the P(3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. More preferably, the P(3HB-co-3HHx) preferably is made up of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
[010] In other embodiments, the extrusion coating is preferably made up of from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxy decanoate.
[Oil] Further, in some instances, the at least one poly(hydroxyalkanoate) is preferably a terpolymer made up from about 75 to about 99.9 mole percent monomer residues of 3- hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3- hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
[012] In certain embodiments, the at least one poly(hydroxyalkanoate) preferably has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
[013] In addition to the poly(hydroxyalkanoate), the extrusion coating may in some instances include an additional compostable polymer. In some embodiments, the extrusion coating preferably includes from about 30.5 weight percent to about 49.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and any mixtures thereof. More preferably, the compostable polymer is made up of poly(lactic acid).
[014] The extrusion coating may also include minor amounts of various additives as well. For instance, in certain embodiments, it is preferred that the extrusion coating also includes from about 0.05 weight percent to about 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
[015] According to certain embodiments, it is also preferred that the extrusion coating includes from about 0.1 weight percent to about 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
[016] In some embodiments, the extrusion coating preferably includes from about 1 weight percent to about 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof. [017] In some embodiments, the extrusion coating also includes from about 0.1 weight percent to about 50 weight percent of at least one compostable impact modifier which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2-ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1,2, 3 -triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), sebacic acid, azelaic acid, cyclohexanedioc acid(CHDA), 1,2 benzenedicarboxylic acid (phthalic anhydride), 1,3 benzenedicarboxylic acid (isophthalic acid), 1,3 benzene dicarboxylic acid (terephthalic acid) and 1,4 butanedioc acid (succinic acid).
[018] In another embodiment, the impact modifier may comprise a polyester made up of at least three different type of monomer residues, which are derived from: (1) isosorbide; (2) succinic acid or anhydride; and (3) 1,3-propanediol.
[019] According to certain embodiments, the extrusion coating preferably exhibits a melt flow rate of about 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTM D1238-13.
[020] Preferably, the extrusion coating is applied over the substrate first side at a coating weight from about 10 to about 50 grams per square meter.
[021] Preferably, the paperboard substrate is made up of Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
[022] Moreover, in some instances, the extrusion coated substrate is preferably formed into a cup, a plate, straw, or a food container. The properties of extrusion coating have been found to be well-suited to such food service uses.
[023] In some instances, the coating preferably exhibits a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter. Further, the coating preferably exhibits a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5. The coating also preferably exhibits a Dyne value greater than 38, measured according to ASTM D2578-04a. [024] In accordance with the present disclosure, it is also preferred that the extrusion coated substrate is home compostable, as determined by ASTM D6868, and/or that the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
DETAILED DESCRIPTION
[025] The present disclosure first provides a home compostable and/or marine degradable extrusion coated substrate.
[026] The substrate is typically paper or a paperboard web. Preferably the paper or paperboard for the substrate comprises Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard. The basis weight for the paper or paperboard substrate is typically at least 400 grams per square meter (gsm) and is more preferably from about 100 gsm to about 400 gsm. The paperboard substrate typically has a thickness from about 1 pt to about 46 pt caliper (about 0.03 mm to about 1.17 mm) and is more preferably from about 5 pt to about 20 pt caliper (about 0.17 mm to about 0.51 mm).
[027] The paperboard substrate includes a first side and a second side. At least the first side of the substrate is coated with the extrusion coating. In some embodiments, both the first side and the second side of the substrate are coated with the extrusion coating.
[028] The extrusion coating which is applied to the first and optionally the second side of the substrate according to the present disclosure is preferably home compostable as defined by ASTM D6868. Preferably the extrusion coating is also biodegradable as defined by ASTM standard D5988.
[029] In general, the extrusion coating comprises at least one poly(hydroxyalkanoate) which is compostable, as well as at least one additional compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), poly(ethylene sebicate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
[030] The amount of the at least one poly(hydroxyalkanoate) in the extrusion coating is generally from about 30 to about 99.5 weight percent of the extrusion coating. More preferably, the extrusion coating is preferably made up of from about 50 to about 69.5 weight percent of the at least one poly(hydroxyalkanoate). [031] A wide range of one poly(hydroxyalkanoates) may be incorporated into the extrusion coating. In some instances, the at least one poly(hydroxyalkanoate) preferably includes poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate (“P(3HB-co-3HHx)”). More preferably, in certain embodiments, the P(3HB-co-3HHx) preferably comprises from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. Even more preferably, this P(3HB-co-3HHx) comprises of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
[032] In other embodiments, the poly(hydroxyalkanoate) may comprise larger monomer units. Thus, in some embodiments, the extrusion coating preferably comprises from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
[033] In still other embodiments, the embodiments, the poly(hydroxyalkanoate) may comprise a terpolymer. For instance, in certain embodiments, the at least one poly(hydroxyalkanoate) is preferably a terpolymer comprising from about 75 to about 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3 -hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
[034] The weight average molecular weight of the at least one poly(hydroxyalkanoate) will preferably range from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
[035] In addition to the poly(hydroxyalkanoate), the extrusion coating also comprises at least one compostable polymer which is selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebicate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof. [036] In general, the extrusion coating comprises from about 5 weight percent to about 69.5 weight percent of this additional compostable polymer. The extrusion coating may in some instances include an additional compostable polymer. In some embodiments, the extrusion coating more preferably comprises from about 30.5 weight percent to about 49.5 weight percent of the at least one compostable polymer.
[037] In general, the additional compostable polymer may be selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof. In certain embodiments, however, the compostable polymer more preferably comprises poly(lactic acid). In other words, the extrusion coating is a blend of poly(lactic acid) with one or more poly(hydroxyalkanoates).
[038] In general, the extrusion coating may also include minor amounts of various additives. In some instances, for example, the extrusion coating also comprises from about 0.05 weight percent to about 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
[039] In certain embodiments, the extrusion coating also preferably comprises from about 0.1 weight percent to about 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
[040] Moreover, the extrusion coating may also comprise from about 1 weight percent to about 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
[041] In some embodiments, the extrusion coating may also comprise from about 0.1 weight percent to about 50 weight percent of at least one impact modifier. In some embodiments, the impact modifier is preferably a compostable polymer which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2-ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1,2, 3 -triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), sebacic acid, azelaic acid, cyclohexanedioc acid(CHDA), 1,2 benzenedicarboxylic acid (phthalic anhydride), 1,3 benzenedicarboxylic acid (isophthalic acid), 1,3 benzene dicarboxylic acid (terephthalic acid) and 1,4 butanedioc acid (succinic acid).
[042] The extrusion coated substrate is formed by first providing a charge of the extrusion coating polymer mixture. Typically, the components of the extrusion coating are combined beforehand and provided in the form of a pelletized resin. A charge of this polymer resin is heated in an extruder to a temperature at or above the melting point of the polymer resin. The exact temperature to which the polymer resin is heated may vary somewhat, depending upon the precise make-up of the polymer resin (the type of compostable polymer, the molecular weight of the compostable polymer, the amount of additives, etc). In general, the polymer resin is heated to a temperature from about 125 °C to about 280 °C, and more preferably heated to a temperature from about 135 °C to about 200 °C.
[043] Once heated, the polymer resin charge is then extruded through a die and applied over a first surface of the substrate. In some instances, a substantially similar process may be used to apply a coating over the second surface of the substrate as well.
[044] According to certain embodiments, the extrusion coating preferably exhibits a melt flow rate of about 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTM D1238-13.
[045] Preferably, the extrusion coating is applied over the substrate first side at a coating weight from about 10 to about 50 grams per square meter.
[046] After the extrusion coating is applied, the finished substrates according to the present disclosure may be used to form a variety of end products. The extrusion coated substrates are particularly well suited to for conversion to form food services items. For instance, the extrusion coated substrates may be formed into a cup, a plate, or a food container. In other embodiments, the extrusion coated substrates may be converted to form cartons, bottles, straws, boxes, or containers.
[047] Again, the extrusion coated substrates according to the present disclosure are well- suited to use for food applications. In particular, the coated substrates exhibit good resistance to oil, grease and to water.
[048] Thus, the extrusion coated substrates of the present disclosure preferably exhibit a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter. Further, the extrusion coated substrates preferably exhibit a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5. Moreover, the extrusion coated substrates also preferably exhibit a Dyne value greater than 38, measured according to ASTM D2578-04a.
[049] At the same time, the extrusion coated substrates of the present disclosure are home-compostable, unlike substrates coated with conventional petroleum-based polymers. In accordance with the present disclosure, it is also preferred that the extrusion-coated substrate is home compostable, as determined by ASTM D6868, and/or that the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
[050] The present disclosure is also further illustrated by the following embodiments:
[051] Embodiment 1. A home compostable and/or marine degradable extrusion coated substrate comprising:
[052] a paperboard substrate having a first side; and
[053] a layer of an extrusion coating applied over at least a portion of the first side, wherein the extrusion coating comprises
[054] from 30 to 99.5 weight percent of at least one poly(hydroxyalkanoate), and
[055] from 5 weight percent to 69.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), poly(ethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof. [056] Embodiment 2. The extrusion coated substrate of Embodiment 1, wherein the extrusion coating comprises from 50 to 69.5 weight percent of the at least one poly(hydroxyalkanoate).
[057] Embodiment 3. The extrusion coated substrate of Embodiments 1 or 2, wherein the at least one poly(hydroxyalkanoate) comprises poly-3 -hydroxybutyrate-co-3 - hydroxyhexanoate (“P(3HB-co-3HHx)”).
[058] Embodiment 4. The extrusion coated substrate of Embodiment 3, wherein the P(3HB-co-3HHx) comprises from 75 to 99 mole percent hydroxybutyrate and from 1 to 25 mole percent hydroxyhexanoate.
[059] Embodiment 5. The extrusion coated substrate of Embodiment 3, wherein the P(3HB-co-3HHx) preferably comprises from 93 to 98 mole percent hydroxybutyrate and from 2 to 7 mole percent hydroxyhexanoate.
[060] Embodiment 6. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating comprises from 1 to 25 weight percent of at least one polyhydroxyalkanoate comprising from 25 to 50 mole percent of hydroxyvalerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
[061] Embodiment 7. The extrusion coated substrate of any of the preceding embodiments, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from 75 to 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from 0.1 to 25 mole percent monomer residues of 3 -hydroxyhexanoate, and from 0.1 to 25 mole percent monomer residues of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
[062] Embodiment 8. The extrusion coated substrate of any of the preceding embodiments, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 50,000 Daltons to 2.5 million Daltons, as determined by ASTM D5296-05.
[063] Embodiment 9. The extrusion coated substrate of any of the preceding embodiments, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 500,000 Daltons to 750,000 Daltons, as determined by ASTM D5296-05.
[064] Embodiment 10. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating comprises from 30.5 weight percent to 49.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and any mixtures thereof.
[065] Embodiment 11. The extrusion coated substrate of any of the preceding embodiments, wherein the at least one compostable polymer comprises poly(lactic acid).
[066] Embodiment 12. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 0.05 weight percent to 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
[067] Embodiment 13. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 0.1 weight percent to 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
[068] Embodiment 14. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 1 weight percent to 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
[069] Embodiment 15. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating further comprises from 0.1 weight percent to 50 weight percent of at least one impact modifier which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2- ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1,2, 3 -triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), sebacic acid, azelaic acid, cyclohexanedioc acid(CHDA), 1,2 benzenedicarboxylic acid (phthalic anhydride), 1,3 benzenedicarboxylic acid (isophthalic acid), 1,3 benzene dicarboxylic acid (terephthalic acid) and 1,4 butanedioc acid (succinic acid).
[070] Embodiment 16. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating exhibits a melt flow rate of 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTMD 1238-13.
[071] Embodiment 17. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating is applied over the substrate first side at a coating weight from 10 to 50 grams per square meter.
[072] Embodiment 18. The extrusion coated substrate of any of the preceding embodiments, wherein the paperboard substrate comprises Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
[073] Embodiment 19. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coated substrate is formed into a cup, a plate, straw, or a food container.
[074] Embodiment 20. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating exhibits a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter.
[075] Embodiment 21. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coating exhibits a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5. [076] Embodiment 22. The extrusion coated substrate of any of the preceding embodiments, wherein the coating exhibits a Dyne value greater than 38, measured according to ASTM D2578-04a.
[077] Embodiment 23. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coated substrate is home compostable, as determined by ASTM D6868.
[078] Embodiment 24. The extrusion coated substrate of any of the preceding embodiments, wherein the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
[079] EXAMPLES
[080] The following non-limiting examples illustrate various additional aspects of the invention. Einless otherwise indicated, temperatures are in degrees Celsius and percentages are by weight based on the dry weight of the formulation.
[081] EXAMPLE 1
[082] To a 40 mm extruder, a mixture of 58.9% 6 mol% PHA, 40% polylactic acid, 0.1% 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane, and 1% Boron Nitride was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[083] EXAMPLE 2
[084] To a 40 mm extruder, a mixture of 58.9% 6 mol% PHA, 40% polybutylene succinate co adipate (PBSA), 0.1% 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane, and 1% Boron Nitride was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[085] EXAMPLE 3
[086] To a 40 mm extruder, a mixture of 58.9% 6 mol% PHA, 20% polybutylene adipate co terephthalate (PBAT), 20% polylactic acid, 0.1% 2,5-Bis(tert-butylperoxy)-2,5- dimethylhexane, and 1% Boron Nitride was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[087] EXAMPLE 4
[088] To a 40 mm extruder, a mixture of 79.9% 2 mol% PHA, 10% polybutylene adipate co terephthalate (PBAT), 10% polylactic acid, 10% polycaprolactone, and 0.1% 2,5- Bis(tert-butylperoxy)-2, 5 -dimethylhexane was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[089] EXAMPLE 5
[090] To a 40 mm extruder, a mixture of 79.9% 2 mol% PHA, 20% polybutylene adipate co terephthalate (PBAT), and 0.1% 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[091] EXAMPLE 6
[092] To a 40 mm extruder, a mixture of 79.9% 2 mol% PHA, 20% polycaprolactone and 0.1% 2, 5 -Bis(tert-butylperoxy)-2, 5 -dimethylhexane was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[093] EXAMPLE 7
[094] To a 40 mm extruder, a mixture of 58.9% 6 mol% PHA, 40% polylactic acid, 0.1% 2, 5 -Bis(tert-butylperoxy)-2, 5 -dimethylhexane, and 1% pentaerythritol was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[095] EXAMPLE 8 [096] To a 40 mm extruder, a mixture of 58.9% 2 mol% PHA, 40% polylactic acid, 0.1% 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane, and 1% pentaerythritol was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[097] EXAMPLE 9
[098] To a 40 mm extruder, a mixture of 59% 6 mol% PHA, 36% polylactic acid, 1% Boron Nitride and 4% polyvinyl alcohol was charged through a feeder into the extruder. Once melted, this mixture was extruded through a die, cut, and cooled to form a plurality of resin pellets for later coating of a substrate.
[099] EXAMPLE 10
[0100] The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 15 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s). Furthermore, the coating exhibits a Cobb test value of 0.17 - 0.21, a Kit test value of 10+, and a Dyne value of 42-44.
[0101] EXAMPLE 11
[0102] The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 12 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0103] EXAMPLE 12
[0104] The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 9 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0105] EXAMPLE 13 [0106] The polymer from Example 1 was applied to light paper with a curtain coater at a coating thickness of 6 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0107] EXAMPLE 14
[0108] The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 15 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0109] EXAMPLE 15
[0110] The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 12 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0111] EXAMPLE 16
[0112] The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 9 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0113] EXAMPLE 17
[0114] The polymer from Example 9 was applied to light paper with a curtain coater at a coating thickness of 6 pounds/ream. The subsequent coating exhibits ease of application and good adhesion verified by 100% fiber tear without additional surface preparation such as flame or corona treatment(s).
[0115] The foregoing description of preferred embodiments for this invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiments are chosen and described in an effort to provide the best illustrations of the principles of the invention and its practical application, and to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.

Claims

WHAT IS CLAIMED IS
Claim 1. A home compostable and/or marine degradable extrusion coated substrate comprising: a paperboard substrate having a first side; and a layer of an extrusion coating applied over at least a portion of the first side, wherein the extrusion coating comprises from 30 to 99.5 weight percent of at least one poly(hydroxyalkanoate), and from 5 weight percent to 69.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate) and mixtures thereof.
Claim 2. The extrusion coated substrate of Claim 1, wherein the extrusion coating comprises from 50 to 69.5 weight percent of the at least one poly(hydroxyalkanoate).
Claim 3. The extrusion coated substrate of Claim 1, wherein the at least one poly(hydroxyalkanoate) comprises poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate (“P(3HB- co-3HHx)”).
Claim 4. The extrusion coated substrate of Claim 3, wherein the P(3HB-co-3HHx) comprises from 75 to 99 mole percent hydroxybutyrate and from 1 to 25 mole percent hydroxyhexanoate.
Claim 5. The extrusion coated substrate of Claim 3, wherein the P(3HB-co-3HHx) preferably comprises from 93 to 98 mole percent hydroxybutyrate and from 2 to 7 mole percent hydroxyhexanoate.
Claim 6. The extrusion coated substrate of Claim 1, wherein the extrusion coating comprises from 1 to 25 weight percent of at least one polyhydroxyalkanoate comprising from 25 to 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxy decanoate.
Claim 7. The extrusion coated substrate of Claim 1, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from 75 to 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from 0.1 to 25 mole percent monomer residues of 3- hydroxyhexanoate, and from 0.1 to 25 mole percent monomer residues of a third 3- hydoxyalkanoate having from 5 to 12 carbon atoms.
Claim 8. The extrusion coated substrate of Claim 1, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 50,000 Daltons to 2.5 million Daltons, as determined by ASTM D5296-05.
Claim 9. The extrusion coated substrate of Claim 1, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 500,000 Daltons to 750,000 Daltons, as determined by ASTM D5296-05.
Claim 10. The extrusion coated substrate of Claim 1, wherein the extrusion coating comprises from 30.5 weight percent to 49.5 weight percent of at least one compostable polymer selected from the group consisting of poly(lactic acid), poly(caprolactone), polyethylene sebecate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and any mixtures thereof.
Claim 11. The extrusion coated substrate of Claim 1, wherein the at least one compostable polymer comprises poly(lactic acid).
Claim 12. The extrusion coated substrate of Claim 1, wherein the extrusion coating further comprises from 0.05 weight percent to 10% of at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
Claim 13. The extrusion coated substrate of Claim 1, wherein the extrusion coating further comprises from 0.1 weight percent to 10 weight percent of at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
Claim 14. The extrusion coated substrate of Claim 1, wherein the extrusion coating further comprises from 1 weight percent to 15 weight percent of at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
Claim 15. The extrusion coated substrate of Claim 1, wherein the extrusion coating further comprises from 0.1 weight percent to 50 weight percent of at least one impact modifier which is the polycondensation reaction product of: (1) a glycol selected from the group consisting of 2-(hydroxymethyl)-2-ethylpropane-l,3-diol (TMP), diethylene glycol, ethylene glycol, 1,6 hexanediol, 2,2 dimethyl 1,3 propanediol (NPG), 1,4 butanediol, 1,3 propanediol, 1,2 propanediol, propane- 1, 2, 3-triol (glycerin), 2-methyl 1,3 propanediol (MPD), and cyclohexanedimethanol; with (2) a carboxylic acid selected from the group consisting of 1,6 hexanedioc acid (adipic acid), 1,12 dodecanedioc acid (DDDA), sebacic acid, azelaic acid, cyclohexanedioc acid(CHDA), 1,2 benzenedicarboxylic acid (phthalic anhydride), 1,3 benzenedicarboxylic acid (isophthalic acid), 1,3 benzene dicarboxylic acid (terephthalic acid) and 1,4 butanedioc acid (succinic acid).
Claim 16. The extrusion coated substrate of Claim 1, wherein the extrusion coating exhibits a melt flow rate of 3 - 10 g/10 min at 190 °C/2.16 kg, as determined by ASTM D 1238- 13.
Claim 17. The extrusion coated substrate of Claim 1, wherein the extrusion coating is applied over the substrate first side at a coating weight from 10 to 50 grams per square meter.
Claim 18. The extrusion coated substrate of Claim 1, wherein the paperboard substrate comprises Kraft paperboard, solid unbleached paperboard, solid bleached sulfate (SBS) paperboard, or a corrugated paperboard.
Claim 19. The extrusion coated substrate of Claim 1, wherein the extrusion coated substrate is formed into a cup, a plate, straw, or a food container.
Claim 20. The extrusion coated substrate of Claim 1, wherein the extrusion coating exhibits a Cobb water absorption value, measured according to TAPPI Standard T441, of less than 30 grams per square meter.
Claim 21. The extrusion coated substrate of Claim 1, wherein the extrusion coating exhibits a Kit Test grease resistance value, measured according to TAPPI Standard T559, of greater than 5.
Claim 22. The extrusion coated substrate of Claim 1, wherein the coating exhibits a Dyne value greater than 38, measured according to ASTM D2578-04a.
Claim 23. The extrusion coated substrate of Claim 1, wherein the extrusion coated substrate is home compostable, as determined by ASTM D6868.
Claim 24. The extrusion coated substrate of Claim 1, wherein the extrusion coated substrate is marine degradable, as determined by ASTM D6691-17.
EP22713804.7A 2021-03-12 2022-03-10 Home compostable and degradable extrusion coated substrates Pending EP4304951A1 (en)

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